Cation-disordered oxides for rechargeable lithium batteries and other applications

ABSTRACT

Embodiments related to cation-disordered lithium metal oxide compounds, their methods of manufacture, and use are described. In one embodiment, a cation-disordered lithium metal oxide includes Li a M b M′ c O 2  with a greater than 1. M includes at least one redox-active species with a first oxidation state n and an oxidation state n′ greater than n, and M is chosen such that a lithium-M oxide having a formula LiMO 2  forms a cation-disordered rocksalt structure. M′ includes at least one charge-compensating species that has an oxidation state y that is greater than n.

RELATED APPLICATIONS

This application claims priority to European Application Serial No.15194519.3, entitled “Cation-Disordered Oxides for Rechargeable LithiumBatteries and Other Applications,” by Ceder, et al., which applicationclaims priority to U.S. Provisional Patent Application Ser. No.62/210,377, entitled “Cation-Disordered Oxides for Rechargeable LithiumBatteries and Other Applications,” by Ceder, et al. The presentapplication also claims priority to said U.S. Pat. Ser. No. 62/210,377.Each of these is incorporated herein by reference in its entirety.

FIELD

Disclosed embodiments are generally related to lithium metal oxides,e.g., for rechargeable lithium batteries or other applications.

BACKGROUND

Certain aspects of the invention relate to a lithium metal oxidecharacterized by a general formula: Li_(a)M_(b)M′_(c)O₂, said lithiummetal oxide comprising a disordered rocksalt LiMO₂ structure enrichedwith Li_(x)M′_(y)O₂ units.

With increasing demand for high-performance lithium ion batteries,cathode materials with high energy density have been sought from diversechemical spaces. In particular, oxide materials have drawn the mostattention because they tend to deliver the highest energy densities.Recently, progress has been made in the oxide space, enlarging thesearch space of high energy density cathode materials tocation-disordered lithium transition metal oxides (Li-TM oxides).

This is known from Komaba et al. who published their work on theLi₃NbO₄-based disordered Li-excess materials [High-capacity electrodematerials for rechargeable batteries: Li₃NbO₄-based system withcation-disordered rocksalt structure, published in PNAS, doi:10.1.073/pnas.1504901112]. Nb appears to have a high valency withintheir compounds, although Komaba et al. did not specify the role of eachspecies in their compounds. In addition, their material does not allowhigh capacity properties to be reached, and further presents poorlyoptimized performance.

SUMMARY

In one embodiment, a lithium metal oxide has a general formulaLi_(a)M_(b)M′_(c)O₂. The lithium metal oxide comprises LiMO₂ andLi_(a)M′_(e)O₂, and the lithium metal oxide has a cation-disorderedrocksalt structure. M includes one or more of a metallic species chosenfrom a group consisting of Ti, V, Cr, Ni, Co, Fe, Mn, Zr, Sb, and Mo,and M is chosen such that LiMO₂ forms a cation-disordered rocksaltstructure. M has a first average oxidation degree n. M′ includes one ormore of a metallic species chosen from a group consisting of Ti, Mo, Cr,W, and Sb, and M′ has a second average oxidation degree y greater thanor equal to n. Further, in some embodiments, 4<32 y<=6, 1<a<=1.4,a+b+c=2, d+e=2, d+(e·y)=4, a+(b·n)+(c·y)=4, 1.3<=d<=1.7, and 0.2<=b<1.

In another embodiment, a lithium metal oxide has a general formula,Li_(a)M_(b)M′_(c)O₂. The lithium metal oxide comprises a disorderedLiMO₂ rocksalt structure enriched or doped with Li_(d)M′_(c)O₂, and thelithium metal oxide has a cation-disordered rocksalt structure. Mcomprises one or more of a metallic species chosen from a groupconsisting of Ti, V, Cr, Ni, Co, Fe, Mn, Zr, Sb, and Mo, and M is chosensuch that LiMO₂ forms a cation-disordered rocksalt structure. M has afirst average oxidation degree n. M′ comprises one or more of a metallicspecies chosen from a group consisting of Ti, Cr, Mn, Zr, Mo, Sn, Sb,and W, and M′ has a second average oxidation degree y greater than orequal to n. Further, 4<=y<32 6, 1<a<=1.4, a+b+c=2, d+e=2, d+(e·y)=4,a+(b·n)+(c·y)=4, 1.3<=d<=1.7, and 0.2<=b<1.

In yet another embodiment, a lithium metal oxide includesLi_(a)M_(b)M′_(c)O₂ having a cation-disordered rocksalt structure. Mincludes at least one redox-active metallic species having a firstoxidation state n and a second oxidation state n′ greater than (>) n,and M′ includes at least one charge-compensating metallic species havingan oxidation state y. In some cases, y may be greater than or equal ton. The value a is greater than 1, and b and c are greater than or equalto 0. Further, M is chosen in some cases such that a lithium-M oxidehaving a formula LiMO₂ forms a cation-disordered rocksalt structure.

In a further embodiment, a lithium metal oxide includesLi_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂ in which 0<x⇐30.

It should be appreciated that tile foregoing concepts, and additionalconcepts discussed below, may be arranged in any suitable combination,as the present disclosure is not limited in this respect. Further, otheradvantages and novel features of the present disclosure will becomeapparent from the following detailed description of various non-limitingembodiments when considered in conjunction with the accompanyingfigures.

BRIEF DESCRIPTION OF DRAWINGS

The accompanying drawings are not intended to be drawn to scale. In thedrawings, each identical or nearly identical component that isillustrated in various figures may be represented by a like numeral. Forpurposes of clarity, not every component may be labeled in everydrawing. In the drawings:

FIG. 1 is a schematic representation of a cation-disorderedrocksalt-type crystal structure;

FIG. 2 shows graphs of X-Ray diffraction patterns ofLi_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂ (x=0, 5, 10, 15, 20)compounds;

FIG. 3 is an SEM micrograph of LNTO;

FIG. 4 is an SEM micrograph of LNTMO5;

FIG. 5 is an SEM micrograph of LNTMO10;

FIG. 6 is an SEM micrograph of LNTMO:15;

FIG. 7 is an SEM micrograph of LNTMO20;

FIG. 8 is an SEM micrograph of LNTMO20 after high-energy ball milling;

FIG. 9 is a graph of the first cycle voltage profiles of LNTO, LNTMO5,LNTMO10, LNTMO15, and LNTMO20;

FIG. 10 is a graph of the capacity change of LNTO, LNTMO5, LNTMO10,LNTMO15, and LNTMO20 over 20 cycles;

FIG. 11 is a graph of the voltage profiles of LNTO for 10 cycles;

FIG. 12 is a graph of the voltage profiles of LNTMO20 for 10 cycles;

FIG. 13 is a graph of the voltage profiles of LNTO when charged anddischarged at 20, 40, 100, 200, and 400 mA/g;

FIG. 14 is a graph of the voltage profiles of LNTMO20 when charged anddischarged at 20, 40, 100, 200, and 400 mA/g;

FIG. 15 is a graph of the first-discharge voltage profile of LNTMO20from a galvanostatic intermittent titration test;

FIG. 16 is a graph of voltage profiles of LNTMO20;

FIG. 17 is a graph of in situ XRD patterns of LNTMO20;

FIG. 18 is a graph of the voltage profile corresponding to the XRDpatterns of FIG. 17;

FIG. 19 is a graph of the lattice parameter corresponding to the XRDpatterns of FIG. 17;

FIGS. 20-22 are graphs of the X-ray absorption near edge spectra of NiK-edge, Ti K-edge, and Mo K-edge, respectively, in LNTMO20;

FIG. 23 is a graph of the electron energy loss spectra of Ti L-edge andO K-edge in LNTMO20;

FIG. 24 is a graph of the first cycle CV profiles of LNTMO20; and

FIG. 25 is a graph of the voltage profile and lattice parameter duringcharge versus the capacity for LNTMO20.

DETAILED DESCRIPTION

Cation-disordered Li-TM oxides such as those described herein mayprovide high capacities and high energy densities when the disorderedLi-TM oxide includes a suitable lithium excess. Without wishing to bebound by theory, a lithium excess may result in the formation of apercolating network of lithium diffusion pathways which allow forimproved electrochemical performance. In some cases, adding excesslithium to a Li-TM oxide results in a relative decrease in the amount ofthe transition metal ions, and therefore the transition metal ions arerequired to transition to a higher oxidation state in order tocompensate the charge, thereby reducing the capacity of the transitionmetal ions to be further oxidized during charge. This in turn may leadto a reduction in the redox capacity of the transition metal ions andtherefore limit the overall electrochemical performance of the Li-TMoxide material.

In view of the above, certain embodiments are generally directed to acation-disordered Li-TM oxide that includes a high-valent chargecompensating species. Without wishing to be bound by theory, a chargecompensating species may allow a redox-active species in the Li-TM oxideto remain at a lower oxidation state, even with a high lithium excess.In this manner, the redox capacity of the redox active species may beincreased, and therefore the overall electrochemical performance of theLi-TM oxide material may be improved.

According to some embodiments, a cation-disordered Li-TM oxide has ageneral formula of Li_(a)M_(b)M′_(c)O₂ in which a has a value greaterthan 1 to provide a lithium excess, M includes at least one redox-activetransition metal species, and M′ includes at least onecharge-compensating transition metal species. Further, the redox-activespecies has a first oxidation state n and a second oxidation state n′,where n′ is greater than n, and the charge compensating species has anoxidation state y that is greater than or equal to n.

In some embodiments, M is chosen such that it forms a cation-disorderedLi-TM oxide without the addition of M′. Specifically, M may include oneor more transition elements in any suitable proportion, chosen such thata lithium-M oxide having a formula LiMO₂ forms a cation-disorderedrocksalt structure. For example, it has been recognized thatLi(NiTi)_(1/2)O₂ forms a cation-disordered rocksalt structure.Therefore, in some embodiments, M includes equal portions of Ni and Ti(i.e., M is (NiTi)_(1/2)). In other embodiments, M may include one ormore of Ti, V, Cr, Ni, Co, Fe, Mn, Zr, Sb, and Mo, one or more of Ti, V,Cr, Ni, Co, Fe, Mn, and Zr, one or more of Ti, V, Cr, Ni, Co, Fe, Mn,Zr, and Sb, one or more of Ti, V, Cr, Ni, Co, Fe, Mn, Zr, and Mo, etc.

It should be understood that a Li-TM oxide material may include anysuitable lithium excess. In some embodiments, a higher lithium excessmay improve performance by providing a more extensive network ofdiffusion channels for lithium ions, which may allow a relatively higherfraction of the lithium ions to move through the material. For example,in the embodiments described above having a formula ofLi_(a)M_(b)M′_(c)O₂, the value a may be greater than or equal to (>=)1.05, greater than or equal to 1.10, greater than or equal to 1.15,greater than or equal to 1.20, or greater than or equal to 1.30, etc. Insome embodiments, a may be less than or equal to (<=) 1.40, less than orequal to 1.30, or less than or equal to 1.20. Combinations of any of theabove ranges for a are also contemplated; for example, a may be betweenor equal to 1.0 and 1.40, 1.05 and 1.30, or any other appropriate range.Further, in certain embodiments, a minimum lithium excess may be neededto achieve a percolating network of lithium diffusion pathways, whichmay be required to achieve a suitable level of electrochemicalperformance. For example, in one embodiment, the minimum lithium excessmay correspond to an a value of about 1.09. However, it should beunderstood that in other embodiments, the minimum lithium content toachieve a percolating network of lithium diffusion pathways maycorrespond to an a value of less than 1.09, or greater than 1.09, as thedisclosure is not so limited.

In some embodiments, b in the above formula may be less than 1. Forexample, b may be less than 0.9, less than 0.8, less than 0.7, less than0.6, or less than 0.5. In addition, b may be greater than or equal to0.2. For instance, h may be greater than or equal to 0.3, greater thanor equal to 0.4, or greater than or equal to 0.5. Combinations of any ofthese are also possible, e.g., b may be between 0.2 and 1. Similarly, insome embodiments, c in the above formula may be less than 1. Forexample, c may be less than 0.9, less than 0.8, less than 0.7, less than0.6, or less than 0.5. In addition, c may be greater than or equal to02. For instance, c may be greater than or equal to 0.3, greater than orequal to 0.4, or greater than or equal to 0.5. Combinations of any ofthese are also possible, e.g., c may be between 0.2 and 1. Moreover, insome embodiments, the values for h and c may be related to the a value.For example, in one embodiment, b may be defined as b=(8−5·a)/3, and cmay be defined as c=[2(a−1)]/3. However, it should be understood thatother relationships between a, b, and c may be possible, as the presentdisclosure is not so limited.

In some embodiments, the compound may be substantially neutrally changed(i.e., electrically neutral), such that the presence of positive species(e.g., Li or transition metals) and negative species (e.g., oxygen)within the compound are balanced. Thus, for example, in the aboveformula, a+b+c may be about 2, and a+(b·n)+(c·y) may be about 4 (basedon compensating the charge of the oxygen ions). In certain embodiments,a compound having a general formula Li_(a)M_(b)M′_(c)O₂ may be describedas a disordered LiMO₂, structure (e.g., a cation-disordered rocksaltstructure) enriched with an appropriate portion of Li_(d)M′_(e)O₂ toform a single phase, cation-disordered structure. For example, d+e maybe about 2, and d+(e·y) may be about 4. In some embodiments, d may bebetween about 1.3 and 1.7, and the proportions of LiMO₂ andLi_(x)M′_(y)O₂ may be chosen appropriately to provide aLi_(a)M_(b)M′_(c)O₂ compound with suitable values for a, b, and c, suchas those described above.

As described above, in some embodiments, M includes at least oneredox-active species having at least a first oxidation state n and asecond oxidation n′, where n′ is greater than n. In some cases, M is atransition metal. For example, in some embodiments, M may include Ni inwhich n is 2+ and n′ is 4+. In other embodiments, M may include at leastone of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sb, and Mo as the redox-activespecies. In certain embodiments, M may include two or more species inany appropriate proportion, with at least one of the species being aredox-active species. For example, in one embodiment, M includes equalportions of Ni and Ti (i.e., M is (NiTi)_(1/2)), with Ni being the redoxactive species. Depending on the particular embodiment, n may have avalue of 2+ and n′ may have a value of 3+, 4+, 5+, or 6+, n may have avalue of 3+ and n′ may have a value of 4+, 5+, or 6+, or n may have avalue of 4+ and n′ may have a value of 5+ or 6+. Moreover, in someembodiments, M may have an average oxidation state between about 2.7 andabout 3.3 (e.g., about 3). For example, in the embodiment describedabove including equal portions of Ni and Ti, M has an average oxidationstate of about 3 (i.e., the equal portions of Ni²⁺ and Ti⁴⁺ ionsprovides an average degree of oxidation of about 3+). In sonic cases,the oxidation state may be at least about 1.8 or at least about 2.7.

Further, according to some embodiments, M′ includes at least onehigh-valent charge-compensating species having an oxidation state y thatis greater than or equal to n. In this manner, the addition of thecharge compensating-species M′ may allow for excess lithium to beincluded in a Li-TM oxide without undesirably causing the redox-activespecies M to move to an oxidation state higher than n. The chargecompensating species may be a transition metal or other atom that canhave a relatively high oxidation state. For example, in someembodiments, M′ may include Mo in which y is 6+. In other embodiments,M′ may include at least one of Ti, Cr, Mn, Zr, Nb, Mo, Sn, Sb, and W. Infurther embodiments, M′ may include at least one of Ti, Cr, Mn, Zr, Mo,Sn, Sb, and W. Depending on the embodiment, y (representing theoxidation state of the charge compensation species) may have a value of,e.g., 4+, 5+, or 6+ or more.

Depending on the particular embodiment, a cation-disordered lithiummetal oxide may have a suitable crystal structure, for example, arocksalt-type structure as is known by those of ordinary skill in theart. For example, FIG. 1 depicts a schematic representation of acation-disordered rocksalt-type structure 100 in accordance with someembodiments. This structure includes oxygen ions 110 arranged in acubic-close-packed sub-lattice, and cations 120 positioned at theoctahedral sites of the oxygen sub-lattice. For example, in theLi_(a)M_(b)M′_(c)O₂ compound described above, the cations 120 may be anyof Li, M, and M′ ions positioned randomly in the octahedral sites of theoxygen sub-lattice. Further, it should be understood that in embodimentsin which M and/or M′ include more than one element, the cations may beany of the elements included in M and/or M′, as discussed herein.Ordered or disordered structures may be identified, for example, usingX-ray diffraction (XRD) or other techniques as discussed herein.

In some embodiments, one or more species may be included in M and/or M′to promote the formation of a desired crystal structure. For example, acompound may include two or more species known to form a disorderedlithium oxide structure. As an illustrative example, Li(NiTi)_(1/2)O₂ isknown to form a disordered rocksalt-type structure, and therefore it maybe desirable to include NiTi as M in the formula Li_(a)M_(b)M′_(e)O₂ tomake a cation-disordered structure energetically favorable.Alternatively, a cation-disordered structure may not be energeticallyfavorable in some embodiments, as the disclosure is not so limited. Insome embodiments, the disordered structure may be a metastable structurethat may be formed via suitable processing.

According to some aspects of the present disclosure, a cation-disorderedLi-TM oxide material as described herein may be used as an electrodematerial in an electrical device, e.g., as a cathode material in arechargeable lithium ion battery. Such cathode materials operate byreversibly releasing (de-intercalation) and reinserting (intercalation)lithium ions during charge and discharge, respectively. As such, thepresence of a percolating network of lithium diffusion pathways,resulting from a lithium excess in the structure, may allow the lithiumions to move easily into and out of the material. As lithium ionsde-intercalate during charge, the redox-active species oxidizes from afirst oxidation state n, towards a higher oxidation state n′. In thismanner, the addition of the charge-compensating species M′ to maintainthe redox-active species in its lower oxidation state n, allows a higherfraction of the redox-active species to be oxidized during charging, andtherefore increases the charge capacity of the Li-TM oxide. Duringdischarge, this process reverses; specifically, lithium ions intercalatethe Li-TM oxide, and the redox-active species is reduced to its first,lower oxidation state n. It should be understood that during chargeand/or discharge, the charge-compensating species may not substantiallychange its oxidation state (i.e., the oxidation state remainssubstantially equal to y during, charge and/or discharge), at least incertain embodiments.

In some embodiments, a redox-active species may not be fully oxidized toa second oxidation state n′ during charge, and instead be may onlypartially oxidized to an intermediate oxidation state between n and n′.Further, in certain embodiments, additional capacity beyond what isprovided by the redox-active species may be provided by other mechanismsduring charge and/or discharge, including, but not limited to, oxygenloss and oxygen oxidation.

According to some embodiments, a Li-TM oxide material according to thepresent disclosure may exhibit a first discharge capacity of greaterthan 50 mAh/g, greater than 75 mAh/g, greater than 100 mAh/g, greaterthan 125 mAh/g, greater than 150 mAh/g, greater than 175 mAh/g, greaterthan 200 mAh/g, or higher when charged and discharged between 1.50 V and4.00 V at 20 mA/g at room temperature. In some embodiments, the Li-TMoxide may exhibit a specific energy density, e.g., of up toapproximately 680 Wh/kg. However, it should be understood that otherdischarge capacities and/or specific energy densities may also bepossible, as the disclosure is not so limited.

As mentioned, in certain embodiments, the crystal structure of acation-disordered Li-TM oxide may be determined and/or confirmed viaX-ray diffraction (XRD) measurements. An XRD pattern may include one ormore characteristic peaks that correspond to a cation-disorderedrocksalt-type structure, such as that described above with regard toFIG. 1. For example, in one embodiment corresponding to a disorderedrocksalt-type structure (Fm-3m space group), an XRD pattern collectedusing Cu Kα radiation may show, over a range of 5 to 70 degrees 2θ (twotheta), a series of peaks with normalized intensity rations l′_(z), withI′_(z)=I_(z)/I₍₁₁₁₎,where I_(z) is the intensity of a peak correspondingto (z) and I₍₁₁₁₎ is the a intensity of a (111) peak. In thisembodiment, when z refers to a (111) peak, I′_(z)=1, when z refers to a(022) peak, 2<=I′_(z)<=5, and when z refers to a (002) peak,4<=1′_(z)<=10. However, it should be understood that other crystaistructures may exhibit different XRD patterns with other peak intensityvalues, as the disclosure is not limited in this regard.

Having generally described the cation-disordered Li-TM oxide materialsand their properties, one possible method for synthesizing thesematerials is described below. However, it is believed that thesematerials may be formed in any of a number of ways, as the currentdisclosure is not limited to any one formation method for thesecompounds.

In one embodiment, for instance, a cation-disordered Li-TM oxidecompound may be prepared by combining one or more suitable precursorstogether, dispersing the precursors in a suitable solvent, milling(e.g., ball milling) the mixture of precursor and solvent, and dryingthe mixture in an oven. The mixture of precursors may be subsequentlypelletized and/or sintered, and then ground, e.g., into a fine powder.Suitable precursor materials may include, but are not limited to,lithium and transition metal salts, and transition metal oxides. Forexample, in some embodiments, Li₂CO₃, Li₂O, NiCO₃, NiO, TiO₂,MoO₂, andMoO₃ may be used as precursors, and acetone or acetonitrile (C₂H₃N) maybe used as the solvent.

European Application Serial No. 15194519.3, entitled “Cation-DisorderedOxides for Rechargeable Lithium Batteries and Other Applications,” byCeder, et al. and U.S. Provisional Patent Application Ser. No.62/210,377, entitled “Cation-Disordered Oxides for Rechargeable LithiumBatteries and Other Applications,” by Ceder, et at are each incorporatedherein by reference in its entirety for all purposes.

NON-LIMITING EXAMPLES

Several non-limiting examples regarding various cation-disordered Li-TMoxides in accordance with the current disclosure are discussed furtherbelow.

In one example, a cation-disordered Li-TM oxide having the generalformula Li_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂ was investigated forx having a value of 0, 5, 10, 15, and 20. In this example, (NiTi)_(1/2)corresponds to M and Mo corresponds to M′ in the Li_(a)M_(b)M′_(c)O₂compound described above, with a=1+x/100, b=1−x/60, and c=x/150.Further, in this example, Ni is the redox-active species with n=2+ andn′=4+, and Mo is the charge-compensating species with y=6+.

To synthesize Li_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂(x=0, 5, 10, 15,20), Li₂CO₃ (Alfa Aesar, ACS, 99% min), NiCO₃ (Alfa Aesar, 99%), TiO₂(Alfa Aesar, 99.9%), and MoO₂ (Alfa Aesar, 99%) were used as precursors.Other than for LiNi_(0.5)Ti_(0.5)O₂ (x=0), a stoichiometric amount ofprecursors were used. For LiNi_(0.5)Ti_(0.5)O₂, 5% excess Li precursorand 4% excess Ni precursor were used, because it resulted in the purestdisordered rocksalt phase with a composition close to the desiredcomposition. The precursors were dispersed into acetone and ball-milledfor 15 hours, and then dried overnight in an oven. The mixture of theprecursors was pelletized and then sintered at 750 degrees C. for twohours in air, followed by furnace cooling to room temperature. After thesintering, the pellets were manually ground into fine powder.

The X-ray diffraction (XRD) patterns for the as-prepared compounds werecollected on a PANalytical multipurpose diffractometer (Cu source) inthe 2θ (two theta) range of 5-85 degrees. Rietveld refinement wascompleted using PANalytical X′pert HighScore Plus software. Scanningelectron microscopy (SEM) images were collected on a Zeiss MerlinHigh-resolution SEM. Elemental analysis of the compounds was performedwith direct current plasma emission spectroscopy (ASTM E 1097-12).

Electron energy loss spectroscopy (EELS) spectra were obtained from thinspecimens on a JEOL 2010F equipped with a Gatan spectrometer, usingparallel incident electron beam and semi-collection angle of 8 mrad inTEM diffraction mode. EELS quantification was performed by using asignal integration window of 50 eV, Hartree-Slater model of partialionization cross section, and power law background subtraction.

For in situ XRD, an in situ cell was designed with a Be window for X-raypenetration. The cell was configured with aLi_(1.2)Ni_(1/3)Ti_(1/3)Mo_(2/15)O₂ electrode film as the workingelectrode, Li metal foil as the counter electrode, 1M of LiPF₆ in EC:DMC(1:1) solution as the electrolyte, and glass fiber as the separator.Galvanostatic charge-discharge of the in situ cell was performed on aSolartron electrochemical potentiostat (SI12287) between 1.5-4.8 V at 10mA/g. The in situ XRD patterns were obtained in one hour intervals froma Bruker D8 Advanced Da Vinci Mo-source diffractometer (Mo source) inthe 2θ (two theta) range of 7-36 degrees. Rietveld refinement on the insitu XRD patterns was performed using PANalytical X′pert HighScore Plussoftware for every other scan.

Ni, Ti, and Mo K-edge ex-situ X-ray absorption near edge spectroscopy(XANES) measurements were performed in transmission made using beamline20 BM at the Advanced Photon Source. The incident energy was selectedusing a Si (111) monochromator. The energy calibration was performed bysimultaneously measuring the spectra of the appropriate metal foil.Harmonic rejection was accomplished using a Rh-coated mirror. Thesamples for the measurements were prepared with theLi_(1.2)Ni_(1/3)Ti_(1/3)Mo_(2/15)O₂ electrode films (a) before cycling,(b) after the first charge to 4.8 V at 20 mA/g, and (c) after the firstcharge to 4.8 V then discharge to 1.5 V at 20 mA/g. The loading densityof the films was ˜5 mg/cm². Additionally, spectra of some referencestandards were measured in transmission mode, to facilitateinterpretation of the XANES data. Data reduction was carried out usingthe Athena software.

To prepare a cathode film for electrochemical characterization, thepowder of the Li—Ni—Ti—Mo oxides and carbon black (Timcal, Super P) werefirst mixed by a planetary ball mill (Retsch PM200) in a weight ratio of70:20 for two hours at 300 rpm. Then, polytetrafluoroethylene (PTFE,DuPont, Teflon 8C) was added to the mixture as a binder, such that thecathode film consisted of the Li—Ni—Ti—Mo oxide powder, carbon black,and PTFE in a weight ratio of 70:20:10. The components were manuallymixed for 30 minutes and rolled into a thin film inside an argon-filledglove box. To assemble a cell for all cycling tests, a 1 M LiPF₆ inethylene carbonate (EC) and dimethyl carbonate (DMC) solution (1:1,Techno Semichem), Celgard 2500 polypropylene separator, and Li metalfoil (FMC) were used as the electrolyte, the separator, and the counterelectrode, respectively. Swa.gelok-type cells were assembled inside anargon-filled glove box and tested on a Maccor 2200 at room temperaturein the galvanostatic mode. Cyclic voltammetry tests were performed on aSolartron electrochemical potentiostat (1470E) between 1.5-4.1 V (or1.5-4.5 V) at 0.1 mV/s. The loading density of the cathode film was ˜5mg/cm². The specific capacity was calculated based on the amount of theLi—Ni—Ti—Mo oxides (70 wt %) in the cathode film.

FIG. 2 shows the XRD patterns of theLi_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂ (x=0, 5, 10, 15, 20)compounds. Hereafter, LiNi_(0.5)Ti_(0.5)O₂ (x=0) will be referred to asLNTO, and Li_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂ with x=5, 10, 15,and 20 will be referred to as LNTMO5, LNTMO10, LNTMO15, and LNTMO20,respectively. The XRD patterns depicted in FIG. 2 are consistent with adisordered rocksalt structure, and the patterns do not show any strongintensity peaks between 2θ (two theta) angles of 16-20 degrees,confirming the (nearly) fully cation-disordered structure with anabsence of obvious short or long range ordering of the cations. Further,the elemental analysis of the compounds summarized in Table 1 show thatthe target phases are successfully synthesized. The insets in FIG. 2 arethe lattice parameters of each compound. The lattice parameter increasesslightly with Li excess. This trend is consistent with the hypotheticalLi _(1.6)Mo_(0.4)O₂ having bigger average cationic radius (0.726 Å) thanLi(NiTi)_(0.5)O₂ (0.704 Å). Thus, introducing excess Li toLi(NiTi)_(0.5)O₂ by incorporating Li_(1.6)Mo_(0.4)O₂ should increase thelattice parameter.

TABLE 1 Li Excess Target Ratio Actual Ratio (%) (Li:Ni:Ti:Mo)(Li:Ni:Ti:Mo) 0 1:0.5:0.5:0 0.99:0.51:0.5:0 5 1.05:.458:.458:0.0331.04:.45:.457:0.035 10 1.1:0.417:0.417:0.067 1.08:0.42:0.43:0.069 151.15:0.375:0.375:0.1 1.15:0.365:0.385:0.1 20 1.2:0.333:0.333:0.1331.2:0.32:0.35:0.135

FIGS. 3-7 show SEM micrographs for LNTO, LNTMO5, LNTMO10, LNTMO15, andLNTMO20, respectively. These SEM results show that small primaryparticles, less than 200 nm in diameter (d), are highly agglomerated insecondary particles for all of the compounds. The average primaryparticle size is the smallest for LNTO (d˜80 nm) and the largest forLNTMO20 (d˜150 nm). FIG. 8 shows an SEM micrograph of the LNTMO20compound after high-energy ball milling with the carbon black (for theelectrode fabrication, as described above). As shown in FIG. 8, afterhigh-energy ball milling, the primary particle size becomes slightlyless than d˜100 nm on average and the size distribution becomes wider.

The cycling performance of the materials was tested by galvanostaticcharge-discharge tests. FIG. 9 shows the first cycle voltage profiles ofLNTO, LNTMO5, LNTMO10, LNTMO15, and LNTMO20 when cycled between 1.5-4.5V at 20 mA/g. The charge-discharge capacity increases with Li excessfrom ˜110 mAh/g to ˜225 mAh/g. The shape of the voltage curves alsoevolves with Li excess, with the beginning of the first charge startingat lower voltage and the 4.3 V plateau becoming longer with higher Liexcess, all of which lead to higher charge capacity. A substantialincrease in the discharge capacity is achieved with higher Li excess.The first discharge capacity of LNTO is only 109 mAh/g, but that ofLNTMO20 is as high as 223 mAh/g. It is notable that the capacity ofLNTMO20 exceeds its theoretical Ni²⁺/Ni⁴⁺ capacity (=201.6 mAh/g),indicating that not only Ni²⁺/Ni⁴⁺ but also other redox couples areactive in LNTMO20. Further, FIG. 10, which depicts the dischargecapacity of the materials as a function of cycle number, demonstratesthat the trend of higher capacity with lithium excess continues uponfurther cycling beyond the first charge cycle.

Since LNTMO20 was found to deliver the best performance among theLi—Ni—Ti—Mo oxides, it was chosen as a representative Li-excess materialand its performance was further compared to that of LNTO. FIGS. 11 and12 show the 10-cycle voltage profiles of LNTO and LNTMO20, respectively,when cycled between 1.5-4.5 V at 20 mA/g. LNTMO20 delivers much highercapacity (˜230 mAh/g) and energy density (˜680 Wh/kg, ˜2800 Wh/l) thanLNTO (˜110 mAh/g, ˜350 Wh/kg, ˜1540 Wh/l). While the capacity above 3 Vis higher for LNTMO20 compared to LNTO, most gains in the dischargecapacity come at voltages lower than 3 V, particularly from the ˜2.2 Vplateau that becomes more obvious with cycling. This results in anaverage discharge voltage of ˜3 V for LNTMO20. It is notable that thecharge-discharge profile of LNTMO20 is asymmetric, with the end ofdischarge voltage being significantly lower for a large fraction of thecapacity than the beginning of charge. This indicates some degree ofkinetic limitation in LNTMO20, although its performance is stillsuperior to that of LNTO.

FIGS. 13-14 depict voltage profiles at various rates for LNTO andLNTMO20, respectively. Cells made of each compound were charged anddischarged once at 10 mA/g, and then at 20, 40, 100, 200, and 400 mA/gfor the subsequent cycles. From the resulting voltage profiles, it isfound that LNTMO20 delivers higher capacity than LNTO at all rates. Asthe rate increases from 10 mA/g to 400 mA/g, the discharge capacitydecreases from 250 mAh/g (750 Wh/kg) to 120 mAh/g (365 Wh/kg) forLNTMO20, and from 120 mAh/g (366 Wh/kg) to 50 mAh/g (145 Wh/kg) forLNTO. Notable, the capacity of LNTMO20 at 400 mA/g is comparable to thatof LNTO at 10 mA/g.

The kinetics in LNTMO20 were analyzed by performing a galvanostaticintermittent titration test (GITT). FIG. 15 shows the first-dischargevoltage profile of LNTMO20 from the GITT. Upon first charge to 270 mAh/gand discharge to 270 mAh/g, every step of 9 mAh/g was galvanostaticallycharged or discharged at 20 mA/g, and then the test cell was relaxed forfive hours between each step. Polarization is most significant at theend of discharge. Voltage relaxation after each discharge step istime-dependent; without wishing to be bound by theory, this may indicatethat the polarization comes mainly from the mass-transfer (Li diffusion)resistance, although other types of resistances such as bysolid-electrolyte interphase (SEI) layers can further contribute to thepolarization. Further, as shown in FIG. 16, the polarization may dependon the charge cutoff voltage. When the cutoff voltage is 4.1 V (solidline), the galvanostatic charge-discharge profiles are symmetric withonly minor polarization. When the material is charged to 4.5 V (dashedline), discharge comes with substantial polarization, which may indicatethat Li diffusion in LNTMO20 depends on structural changes that mayoccur at high voltage.

In situ X-ray diffraction (XRD) was performed to investigate thestructural evolution of LNTMO20 upon charge and discharge. FIG. 17 showsthe in situ XRD patterns of LNTMO20 upon two galvanostaticcharge-discharge cycles between 1.5-4.8 V at 10 mA/g. The correspondingvoltage profile and the lattice parameters from single-phase XRDrefinements are shown in FIG. 18 and FIG. 19, respectively. During thefirst charge, the lattice parameter decreases with three distinctregimes as evidenced by the (002) peak shifting to a higher angle. Forthe first ˜110 mAh/g of charge accompanying the sloped voltage profile,the peak continuously shifts to a higher angle. However, further peakshift is negligible up to a charge of ˜215 mAh/g, along the 4.3 Vplateau. After this region, the peak further shifts to a higher anglewith charging. Without wishing to be bound by theory, this may indicatethat the disordered lattice shrinks at the beginning and end of thefirst charge, but there is an interval in the middle where it does notshrink significantly. During the first discharge, the (002) peak rapidlyshifts to a lower angle by discharging to ˜100 mAh/g, but any furthershift is small. After the first discharge, the peak is at a lower angle(˜19.6 degrees) than where it was before cycling (˜19.8 degrees),showing expansion of LNTMO20 after the first cycle. During the secondcycle, the lattice parameter decreases upon charge and increases upondischarge until the 2.2 V plateau is reached, after which the latticeexpansion is small.

X-ray absorption near edge spectroscopy (XANES) measurements wereperformed to study the redox mechanisms of LNTMO20. FIGS. 20-22 show theNi K-edge, Ti K-edge, and Mo K-edge XANES spectra of LNTMO20,respectively. Each figure shows spectra before cycling (black), afterthe first charge to 4.8 V (blue: ˜300 mAh/g charged), and after thefirst discharge to 1.5 V (red: ˜250 mAh/g discharged). From FIG. 20, itis seen that the Ni edge shifts from an energy close toLiNi_(2/3)Sb_(1/3)O₂ used as a standard for Ni²⁺ to a higher energysimilar to Ni³⁺ in NaNiO₂ upon first charge to 4.8 V. After the firstdischarge to 1.5 V, the Ni edge returns to its starting position.Without wishing to be bound by theory, this may indicate that Ni²⁺ isoxidized up to Ni^(˜3+) upon first charge to 4.8 V, then reduces back toNi²⁺ after the first discharge. As the Ni²⁺/Ni³⁺ capacity corresponds to˜100 mAh/g, this finding may suggest that the remaining charge capacitycomes from either oxygen loss and/or oxygen oxidation, both of which areknown to occur in Li-excess materials.

From the absorption spectra shown in FIGS. 21-22, it is seen that the Tiand Mo edges do not shift significantly during charging and discharging.This may indicate that changes in the Mo and Ti oxidation states duringthe cycle, if any, are small on average. However, the pre-edge peak ofMo XANES at ˜20006 eV increases in intensity after the first charge, andremains at higher intensity after the first discharge. It has beenpreviously shown that the intensity of the pre-edge peak increases asthe site symmetry of the transition metal ions decreases from acentrosymmetric to a non-centrosymmetric environment. This may bebecause an electric dipole-forbidden transition from the Mo 1s to the Mo4d orbital (corresponding to the pre-edge peak) becomes partiallyallowed in a non-centrosymmetric environment which leads to stronger4d-5p mixing. For example, the pre-edge peak observed in MoO₃(dot-dashed line) originates from highly distorted Mo-O octahedra.Therefore, the intensity increase of Mo pre-edge peak of LNTMO20 showsthat the Mo environment deviates from the regular octahedralcoordination upon cycling, which may originate from a distortion of theMo-O octahedra, or from some degree of Mo⁶⁺ migration from octahedral totetrahedral sites. Comparison with the spectra of MoO₂ and MoO₃ showsthat the Mo edge position of LNTMO20 does not shift down in energy afterthe first discharge, which strongly suggests that the majority of the Moions remain 6+. Likewise, any reduction in the Ti oxidation state ondischarge is small on average. However, it is noted that XANES collectsinformation from the entire bulk particles. Therefore, changes in theoxidation states in the surface or near surface regions might not beclearly visible in the ensemble-averaged XANES spectra.

To investigate if oxygen loss occurs from LNTMO20, electron energy lossspectroscopy (EELS) was performed on the surface of the LNTMO20particles before and after cycling. FIG. 23 shows the Ti L-edge and OK-edge from the EELS spectra of LNTMO20 before cycling (black) and after20 cycles (red) between 1.5-4.5 V at 20 mA/g. Comparing the EELSquantifications of the atomic ratio of O to Ti, a considerable decreasein the ratio by ˜39% is found after cycling. Without wishing to be boundby theory, this may indicate that oxygen loss has occurred from thesurface of LNTMO20 upon cycling, which may contribute to additionalcharge capacity beyond the Ni²⁺/Ni^(˜3+) capacity. In addition, it isobserved that the Ti L-edge is chemically shifted towards lower energyby ˜1.5 eV relative to the O K-edge after cycling as shown in the insetin FIG. 23), which may indicate Ti reduction below 4+ at the surfaceregion.

Oxygen loss from LNTMO20 may also be inferred from the cyclicvoltammetry (CV) tests. FIG. 24 shows the first cycle CV profiles ofLNTMO20. When the oxidation cutoff voltage is 4.1 V (red), a mainreduction peak is observed at ˜3.7 V and a minor reduction peak isobserved at ˜2.7 V. However, when the cutoff is increased to 4.5 V(black), an additional reduction peak at ˜2.2 V is observed in the CVprofile. Without wishing to be bound by theory, this is likelyassociated with reduction of a second transition metal species andresponsible for the discharge plateau at ˜2.2 V upon galvanostaticcycling between 1.5-4.5 V (FIG. 12). This shows that charging above 4.1V may trigger a reaction which, upon discharge, allows reduction of aspecies that was previously not reducible. In the case of LNTMO20,reduction of MO⁶⁺ or Ti⁴⁺ upon discharge is likely triggered by oxygenloss. Although the Mo and Ti XANES do not show clear evidence of thedecrease in the average Mo and Ti oxidation states after the firstdischarge (FIGS. 21 and 22), the apparent discrepancy between CV (orEELS) and XANES suggests that oxygen loss may be significant at thesurface but not in the bulk.

Based on the above-described results from the XANES spectra, the limitfor the oxygen loss capacity of LNTMO20 during the first cycle isapproximated. The Ni XANES shows that Ni²⁺ is oxidized to Ni^(˜3+) uponfirst charge to 4.8 V, which gives ˜100 mAh/g in capacity (FIG. 20). Asdiscussed above, the remaining first charge capacity (˜200 mAh/g) mayoriginate from oxygen loss and/or oxygen oxidation. Without wishing tobe bound by theory, this proposed mechanism is consistent with thechange in the lattice parameter of LNTMO20 during the first charge asshown in FIG. 25. Upon first charge to ˜110 mAh/g, the lattice parameterdecreases continuously. This may be explained with the Ni²⁺/Ni⁻³⁺oxidation (˜100 mAh/g) because Ni³⁺ (r=0.56 Å) and Ni⁴⁺ (r=0.48 Å) aresmaller than Ni²⁺ (r=0.69 Å). Upon further charge to ˜215 mAh/g, thelattice parameter barely decreases. This can be related to oxygen lossbecause charging with oxygen loss may slow down the increase in theoxidation states of the remaining ions in the crystal structure. It isnoted that the capacity in this region is ˜105 mAh/g, which roughlyagrees with the maximum estimated oxygen loss capacity (˜90 mAh/g) fromthe XANES results discussed above. Finally, charging beyond ˜215 mAh/gdecreases the lattice parameter. This may be explained by oxygenoxidation which shrinks the oxygen framework either by making the oxygenions smaller in size or by introducing peroxo-like species whoseoxygen-to-oxygen bond distance is shorter.

While several embodiments have been described and illustrated herein,those of ordinary skill in the art will readily envision a variety ofother means and/or structures for performing the functions and/orobtaining the results and/or one or more of the advantages describedherein, and each of such variations and/or modifications is deemed to bewithin the scope of the present disclosure. More generally, thoseskilled in the art will readily appreciate that all parameters,dimensions, materials, and configurations described herein are meant tobe exemplary and that the actual parameters, dimensions, materials,and/or configurations will depend upon the specific application orapplications for which the teachings of the present invention is/areused. Those skilled in the art will recognize, or be able to ascertainusing no more than routine experimentation, many equivalents to thespecific embodiments of the invention described herein. It is,therefore, to be understood that the foregoing embodiments are presentedby way of example only and that, within the scope of the appended claimsand equivalents thereto; the disclosure may be practiced otherwise thanas specifically described and claimed. The present disclosure isdirected to each individual feature, system, article, material, kit,and/or method described herein. In addition, any combination of two ormore such features, systems, articles, materials, kits, and/or methods,if such features, systems, articles, materials, kits, and/or methods arenot mutually inconsistent, is included within the scope of the presentinvention.

All definitions, as defined and used herein, should be understood tocontrol over dictionary definitions, definitions in documentsincorporated by reference, and/or ordinary meanings of the definedterms.

The indefinite articles “a” and “an,” as used herein in thespecification and in the claims, unless clearly indicated to thecontrary, should be understood to mean “at least one.”

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesarid disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e. “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.” “Consisting essentially of,” when used in the claims,shall have its ordinary meaning as used in the field of patent law.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from any one or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

When the word “about” is used herein in reference to a number, it shouldbe understood that still another embodiment of the invention includesthat number not modified by the presence of the word “about.”

It Should also be understood that, unless clearly indicated to thecontrary, in any methods claimed herein that include more than one stepor act, the order of the steps or acts of the method is not necessarilylimited to the order in which the steps or acts of the method arerecited.

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the United States Patent Office Manual ofPatent Examining Procedures, Section 2111.03.

Some preferred embodiments are as follows:

1. A lithium metal oxide having a general formula: LiaMbM′cO2, saidlithium metal oxide comprising LiMO2 and LidM′eO2, said lithium metaloxide having a cation-disordered rocksalt structure, wherein M comprisesone or more of a metallic species chosen from a group consisting of Ti,V, Cr, Ni, Co, Fe, Mn, Zr, Sb, and Mo, M being chosen such that LiMO2forms a cation-disordered rocksalt structure, and M having a firstaverage oxidation degree n, wherein M′ comprises one or more of ametallic species chosen from a group consisting of Ti, Cr, Mn, Zr, Mo,Sn, Sb, and W, and M′ having a second average oxidation degree y greaterthan or equal to n, with 4<=y<=6, and wherein 1<a<=1.4, a+b+c=2, d+e=2,d+(e·y)=4,a+(b·n)+(c·y)=4, 1.3<=d<=1.7, and 0.2<=b <1.

2. The lithium metal oxide of embodiment 1, wherein n is between 2.7 and3.3.

3. The lithium metal oxide of any one of embodiments 1-2, wherein n isabout 3.

4. The lithium metal oxide of any one of embodiments 1-3, wherein M′ isone or more of a metallic species chosen from a group consisting of Moand Cr, and wherein b=(8-5a)/3, c=[2(a−1)]/3, d=1.6, and e=0.4.

5. The lithium metal oxide of any one of embodiments 1-4, wherein M isan alloy of Ni and Ti in a 1:1 molar ratio.

6. The lithium metal oxide of any one of embodiments 1-5, wherein M′ isMo and y is equal to 6.

7. The lithium metal oxide of any one of embodiments 1-6, wherein XRD ofthe lithium metal oxide collected using Cu Kα radiation shows, in arange 5-70 degrees of 2θ (2 theta), a series of normalized intensityratios I′z, with I′z=Iz/I(111). Iz being an first intensity of a (z)peak and I(111) being a second intensity of a (111) peak, wherein when zrefers to a (111) peak, I′z=1, when z refers to a (022) peak, 2<I′z<5,and when z refers to a (002) peak, 4<I′z<10, wherein said series ofnormalized intensity ratios I′z corresponds to a disordered rocksaltLiMO2 structure having a Fm-3 m space group.

8. The lithium metal oxide of any one of embodiments 1-7, wherein thelithium metal oxide has a lattice parameter greater than or equal to 4Angstroms.

9. The lithium metal oxide of any one of embodiments 1-8, wherein thelattice parameter is between 4.13 Angstroms and 4.15 Angstroms.

10. The lithium metal oxide of any one of embodiments 1-9, wherein thelithium metal oxide has a first capacity greater than 109 mAh/g whencharged and discharged between 1.5 and 4.5V at 20 mA/g at roomtemperature.

11. The lithium metal oxide of any one of embodiments 1-10, wherein thelithium metal oxide has a first capacity greater than 150 mAh/g whencharged and discharged between 1.5 and 4.5V at 20 mA/g at roomtemperature.

12. The lithium metal oxide of any one of embodiments 1-11, wherein thelithium metal oxide presents a single phase cation-disordered rocksaltstructure.

13. An electrical device, comprising an electrode comprising the Lithiummetal oxide of any one of embodiments 1-12.

14 A lithium metal oxide comprising: LiaMbM′cO2 having acation-disordered rocksalt structure, wherein M comprises at least oneredox-active metallic species having a first oxidation state n and asecond oxidation state n′ greater than n, M′ comprises at least onecharge-compensating metallic species having an oxidation state y greaterthan or equal to n, a is greater than 1, and b and c are greater than orequal to 0, and wherein M is chosen such that a lithium-M oxide having aformula LiMO2 has a cation-disordered rocksalt structure.

15. The lithium metal oxide of embodiment 14, wherein at least some ofthe M is in the first oxidation state.

16. The lithium metal oxide of any one of embodiments 14-15, wherein atleast some of the M is in the second oxidation state.

16. The lithium metal oxide of any one of embodiments 14-16, wherein nis at least 2.7

18. The lithium metal oxide of any one of embodiments 14-17, wherein yis at least 4.

19. The lithium metal oxide of any one of embodiments 14-18, wherein yis at least 5.

20. The lithium metal oxide of any one of embodiments 14-19, wherein yis at least 6.

21. The lithium metal oxide of any one of embodiments 14-20, wherein Mincludes at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sb, and Mo.

22. The lithium metal oxide of any one of embodiments 14-21, wherein Mincludes at least Ni and Ti.

23. The lithium metal oxide of any one of embodiments 14-22, wherein Mincludes equal portions of Ni and Ti.

24. The lithium metal oxide of any one of embodiments 14-23, wherein M′includes at least one of Ti, Cr, Mn, Zr, Mo, Sn, Sb, and W.

25. The lithium metal oxide of any one of embodiments 14-24, wherein ais less than or equal to 1.4.

26. The lithium metal oxide of any one of embodiments 14-25, wherein theLiaMbM′cO2 has a first discharge capacity of at least 150 mAh/g whencharged and discharged between 1.5 V and 4.5 V at 20 mA/g at roomtemperature.

27. The lithium metal oxide of embodiment 26, wherein the firstdischarge capacity is at least 200 mAh/g.

28. An electrical device, comprising an electrode comprising the lithiummetal oxide of any one of embodiments 14-27.

29. A lithium metal oxide comprising Li1+x/100(NiTi)1/2−x/120Mox/150O2,wherein 0<x<=30.

30. The lithium metal oxide of embodiment 29, wherein x is about 20.

31. The lithium metal oxide of any one of embodiments 29-30, wherein thelithium metal oxide has a first discharge capacity of at least 150 mAh/gwhen charged and discharged between 1.5 V and 4.5 V at 20 mA/g at roomtemperature.

32. The lithium metal oxide of embodiment 31, wherein the firstdischarge capacity is at least 200 mAh/g.

33. An electrical device, comprising an electrode comprising the lithiummetal oxide of any one of embodiments 29-32.

34. A lithium metal oxide having a general formula: LiaMbM′cO2, saidlithium metal oxide comprising a disordered LiMO2 rocksalt structureenriched with LidM′eO2, said lithium metal oxide having acation-disordered rocksalt structure, wherein M comprises one or more ofa metallic species chosen from a group consisting of Ti, V, Cr, Ni, Co,Fe, Mn, Zr, Sb, and Mo, M being chosen such that LiMO2 forms acation-disordered rocksalt structure, and M having a first averageoxidation degree n, wherein M′ comprises one or more of a metallicspecies chosen from a group consisting of Ti, Cr, Mn, Zr, Mo, Sn, Sb,and W, and M′ having a second average oxidation degree y greater than orequal to n, with 4<=y<=6, and wherein 1<a<=1.4, a+b+c=2, d+e=2,d+(e·y)=4, a+(b·n)+(c·y)=4, 1.3<=d <=1.7, and 0.2<=b<1.

35. The lithium metal oxide of embodiment 34, wherein n is between 2.7and 3.3.

36. The lithium metal oxide of any one of embodiments 34-35, wherein nis about 3.

37. The lithium metal oxide of any one of embodiments 34-36, wherein M′is one or more of a metallic species chosen from a group consisting ofMo and Cr, and wherein b=(8−5a)/3, c=[2(a−1)]/3, d=1.6, and e=0.4.

38. The lithium metal oxide of any one of embodiments 34-37, wherein Mis an alloy of Ni and Ti in a 1:1 molar ratio.

39. The lithium metal oxide of any one of embodiments 34-38, wherein M′is Mo and y is equal to 6.

40. The lithium metal oxide of any one of embodiments 34-39, wherein XRDof the lithium metal oxide collected using Cu Kα radiation shows, in arange 5-70 degrees of 2θ (2 theta), a series of normalized intensityratios I′z, with I′z=Iz/I(111), Iz being an first intensity of a (z)peak and I(111) being a second intensity of a (111) peak, wherein when zrefers to a (111) peak, I′z=1, when z refers to a (022) peak, 2<I′z<5,and when z refers to a (002) peak, 4<I′z<10, wherein said series ofnormalized intensity ratios I′z corresponds to a disordered rocksaltLiMO2 structure having a Fm-3 m space group.

41. The lithium metal oxide of any one of embodiments 34-40, wherein thelithium metal oxide has a lattice parameter greater than or equal to 4Angstroms.

42. The lithium metal oxide of any one of embodiments 34-41, wherein thelattice parameter is between 4.13 Angstroms and 4.15 Angstroms.

43. The lithium metal oxide of any one of embodiments 34-42, wherein thelithium metal oxide has a first capacity greater than 109 mAh/g whencharged and discharged between 1.5 and 4.5V at 20 mA/g at roomtemperature.

44. The lithium metal oxide of any one of embodiments 34-43, wherein thelithium metal oxide has a first capacity greater than 150 mAh/g whencharged and discharged between 1.5 and 4.5V at 20 mA/g at roomtemperature.

45. The lithium metal oxide of any one of embodiments 34-44, wherein thelithium metal oxide presents a single phase cation-disordered rocksaltstructure.

46. An electrical device, comprising an electrode comprising the lithiummetal oxide of any one of embodiments 34-45.

1. A lithium metal oxide having a general formula: Li_(a)M_(b)M′_(c)O₂, said lithium metal oxide comprising LiMO₂ and Li_(d)M′_(e)O₂, said lithium metal oxide having a cation-disordered rocksalt structure, wherein M comprises one or more of a metallic species chosen from a group consisting of Ti, V, Cr, Ni, Co, Fe, Mn, Zr, Sb, and Mo, M being chosen such that LiMO₂ forms a cation-disordered rocksalt structure, and M having a first average oxidation degree n, wherein M′ comprises one or more of a metallic species chosen from a group consisting of Ti, Cr, Mn, Zr, Mo, Sn, Sb, and W, and M′ having a second average oxidation degree y greater than or equal to n, with 4<=y<=6, and wherein 1<a<=1.4, a+b+c=2, d+e=2, d+(e·y)=4, a+(b·n)+(c·y)=4, 1.3<=d<=1.7, and 0.2<=b<1. 2-47. (canceled)
 48. The lithium metal oxide of claim 1 wherein said disordered LiMO₂ rocksalt structure is enriched with Li_(d)M′_(e)O₂.
 49. The lithium metal oxide of claim 1, comprising Li_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂, and wherein 0<x<=30.
 50. The lithium metal oxide of claim 1, wherein n is between 2.7 and 3.3.
 51. The lithium metal oxide of claim 1, wherein M′ is one or more of a metallic species chosen from a group consisting of Mo and Cr, and wherein b=(8−5a)/3, c=[2(a−1)]/3, d=1.6, and e=0.4.
 52. The lithium metal oxide of claim 1, wherein M is an alloy of Ni and Ti in a 1:1 molar ratio and/or M′ is Mo and y is equal to
 6. 53. The lithium metal oxide of claim 1, wherein XRD of the lithium metal oxide collected using Cu Kα (K alpha) radiation shows, in a range 5-70 degrees of 2θ (2 theta), a series of normalized intensity ratios I′z, with I′z=Iz/I(111), Iz being an first intensity of a (z) peak and I(111) being a second intensity of a (111) peak, wherein when z refers to a (111) peak, I′z=1, when z refers to a (022) peak, 2 <I′z<5, and when z refers to a (002) peak, 4<I′z<10, wherein said series of normalized intensity ratios I′z corresponds to a disordered rocksalt LiMO₂ structure having a Fm-3 m space group.
 54. The lithium metal oxide of claim 1, wherein the lithium metal oxide has a lattice parameter greater than or equal to 4 Angstroms.
 55. The lithium metal oxide of claim 1, wherein the lithium metal oxide has a first capacity greater than 109 mAh/g when charged and discharged between 1.5 and 4.5V at 20 mA/g at room temperature.
 56. The lithium metal oxide of claim 1, wherein the lithium metal oxide presents a single phase cation-disordered rocksalt structure.
 57. The lithium metal oxide of claim 1, wherein the lattice parameter is between 4.13 Angstroms and 4.15 Angstroms.
 58. The lithium metal oxide of claim 1, wherein the lithium metal oxide has a first capacity greater than 150 mAh/g when charged and discharged between 1.5 and 4.5V at 20 mA/g at room temperature.
 59. An electrical device, comprising an electrode comprising the lithium metal oxide of claim
 1. 60. A lithium metal oxide comprising Li_(1+x/100)(NiTi)_(1/2−x/120)Mo_(x/150)O₂, wherein 0<x<=30.
 61. A lithium metal oxide comprising: Li_(a)M_(b)M′_(c)O₂ having a cation-disordered rocksalt structure, wherein M comprises at least one redox-active metallic species having a first oxidation state n and a second oxidation state n′ greater than n, M′ comprises at least one charge-compensating metallic species having an oxidation state y greater than or equal to n, a is greater than 1, and b and c are greater than or equal to 0, and wherein M is chosen such that a lithium-M oxide having a formula LiMO₂ has a cation-disordered rocksalt structure.
 62. The lithium metal oxide of claim 61, wherein n is at least 1.8.
 63. The lithium metal oxide of claim 61, wherein y is at least
 4. 64. The lithium metal oxide of claim 61, wherein M includes at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sb, and Mo.
 65. The lithium metal oxide of claim 61, wherein M′ includes at least one of Ti, Cr, Mn, Zr, Mo, Sn, Sb, and W.
 66. The lithium metal oxide of claim 61, wherein a is less than or equal to 1.4. 